Pesticidal benzisoxazolo (thiono) phosphoric (phosphonic) acid esters

ABSTRACT

Benzisoxazolo(thiono)phosphoric(phosphonic)acid esters of the general formula   IN WHICH R is a lower alkyl radial, R1 is a lower alkyl or alkoxy radical, and X is an oxygen or sulfur atom, WHICH POSSESS INSECTICIDAL, ACARICIDAL, NEMATOCIDAL AND, IN SOME CASES, FUNGICIDAL PROPERTIES.

United States Patent Lorenz et al.

[451 Sept. 23, 1975 PESTICIDAL BENZISOXAZOLO (THIONO) PHOSPHORIC(PHOSPHONIC) ACID ESTERS Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany Filed: Mar. 8, 1974 Appl. No.: 449,581

Related US. Application Data Division of Ser. No. 151,515, June 9, 1973,Pat. No.

Foreign Application Priority Data June 26, 1970 Germany 2031750 US. Cl.424/200 Int. Cl. A01N 9/36 Field of Search 424/200; 260/307 D ReferencesCited FOREIGN PATENTS OR APPLICATIONS 8/1964 United Kingdom PrimaryExaminerAlbert T. Meyers Assistant Examinerl .eonard Schenkman Attorney,Agent, or Firm-Burgess, Dinklage & Sprung [57] ABSTRACTBenzisoxazolo(thiono)phosphoric(phosphonic )acid esters of the generalformula in which R is a lower alkyl radial, R is a lower alkyl or alkoxyradical, and X is an oxygen or sulfur atom,

which possess insecticidal, acaricidal, nematocidal and, in some cases,fungicidal properties.

6 Claims, No Drawings j3 -hydroxy-l ,Z-benzisoxazole of the formula formof an appropriate alkali metal salt, alkaline earth V 1 2 PESTICIDALBENZISOXAZOLO (THIQNO) I i no a PHOSPHORIC (PHOSPHONIC) ACID ESTERS RP-fla1 (In) This is a division of application Ser. No. 15 l ,5 l5 filedJune 9, 1971 now U.S.'Pat. No. 3,828,063. 5

The present invention relates to and has for its obin which jects theprovision of particular new benzisoxazolo(th R, R and X possess themeaning stated above, and ion'o) phosphoric(phosphonic) acid esters,which pos- Hal is a halogen atom. sess insecticidal, gearicidal,nematocidal and fungicidal Surprisingly, thebenzisoxazolo(thiono)phosphoric properties, active compositions in theform of mixtures (phosphonic) acid esters according to the invention ofsuch compounds with solid and liquid dispersible show a considerablyhigher insecticidal and acaricidal 'l Vehicles, and methods forProdllelng suel'l activity than the known halogen-substituted benzisox-P u and using such Compounds-in a new y azolo(thiono) phosphoric acidesters which are the Pe y combating Pests, -ginsects, Searlds,chemically most closely comparable active compounds ed and fungi, p i ylnseets, aeal'lds and nemal5 of the same direction of activity. Thesubstances actodesrwith Mlle!v and further Objects m g PP cording to theinvention therefore represent a genuine ent from a'study of the withinspecification and accomenrichment f th t P ny g P lf3-hydroxy-l,Z-benzisoxazole and 0,0-diethylth- From German PublishedSpeelfieatlen l,253,7 l 3 it is iono-phosphoric acid ester chloride areused as starting. known that halogen-substituted.benzisoxazolothiono- 2Oi l th a ti n course can be represented by phosphoric (phosphonic) acidesters, such as 0,0- h f llo ing ti (I, I i acid acc' to: QIEF C1-P(0C Hf3 n 1 --xc1 1 ,s on 1 -P(OC H (Ni dimethylordiethyl-O-[5-chlorobenzisoxazol(3)yl]- Advantageously the alkyl oralkoxy groups of R and thionophosphoric acid ester, exhibit aninsecticidal ac- R contain 1 to 4-carbon atoms and, preferably, R istivity. methyl or ethyl and R is methyl, ethyl, methoxy or eth- Thepresent invention provides, as new compounds, oxy; Hal is preferably achlorine atom. the benzisoxazolo (thiono)phosphoric )phosphonic) AS x pof )P P (P P id esters of h general f l 7 acid ester halides (III) whichcan be used, there may be mentioned: 0,0-dimethyl-, 0,0-diethyl-, 0,0-diisopropyl-, O-methyl- O-ethyb, O-ethyl-O-isopropyl- I 40 andO-methyl-O-isopropyl-phosphoric acid ester halides .I N v and theirthiono analogues; further, O,P-dimethyl-, f i f (1)" Q,P-diethyl-,'O,'P-diisopropyl, O-methyl-P-ethyl-, O-methyl-P-isopropylO-isopropyl-P-ethyland O- isopropyl-P-methyl-phosphonic acid esterhalides and in'which v their thiono'analogues. I

R is er alky d v v The (thiono)phosphoric(phosphon1c) acid ester havR isa a lower alkyl or alkoxy radical, and

X is an oxygen or sulfur atom. The compounds of the present inventionshow strong insecticidal, acaricidal, nematocidal, and, in some cases,fungicidal, properties.

The present invention also provides a process for the preparation of abenzisoxazolo(thiono )phosphoric (phosphonic) acid esterof the formula(I) in which as starting'materials can .be prepared according to knownprocesses.

The reaction may be carried out in a solvent or diluent; practically allinert organic solvents are suitable.

Preferred solvents are aliphatic and aromatic optionally chlorinatedhydrocarbons, such as benzene, toluene, xylenes, benzine, methylenechloride, chloroform, carbon tetrachloride and chlorobenzene; ethers,such such as acetone, methylethyl ketone, methylisopropyl ketone andmethylisobutyl ketone; and nitriles, such as acetonitrile.

As acid-acceptors, all customary acid-binding agents are suitable.Especially suitable are alkali metal carp bonates and alcoholates, suchas sodium or potassium is reacted in the Presence of an add-acceptor inthe carbonate and sodium or potassium methylate or ethyl- 65 ate;furthermore, aliphatic, aromatic or heterocyclic metal salt or ammoniumsalt, th a 0 )P amines, for example triethylamine, dimethylamine, diph r(p p field ester halide 0f the general methylaniline,dimethylbenzylamin'e or pyridine, may formula v 1 be used.

lides as well as the 3-hydroxybenzisoxazole to be used,

as diethyl ether, dibutyl ether and dioxane; ketones,

The reaction temperatures can be varied within a fairly wide range. ingeneral, the reactants are mixed at about to 50C, preferably at about 30to 35C, and the mixture is afterwards stirred at about 50 to 120C,preferably at about 70 to 80C.

The reaction is, in general, carried out at normal pressure.

When carrying out the process, the starting materials are, in mostcases, reacted in equimolar amounts in one of the above-mentionedsolvents at elevated temperatures. An excess of one or other of thereactants brings no substantial advantages. The heterocyclic reactantcan also be used in the form of its alkali metal salts, alkaline earthmetal salts or ammonium salt, as already mentioned. The reactionsolution is in most cases afterwards stirred for some hours at elevatedtemperatures, taken up in benzene and worked up as usual.

The esters according to the invention are obtained in most cases in theform of colorless to slightly yellowcolored, viscous, water-insolubleoils which cannot be distilled without decomposition but can, byso-called slight distillation, that is by prolonged heating tomoderately elevated temperatures under reduced pressure, be freed fromthe last volatile components and in this way by purified. For theircharacterization, the refractive index is especially useful.

The new compounds according to the invention are distinguished byoutstanding nematocidal, insecticidal and acaricidal properties. Theyare effective against both sucking and biting insects,, Diptera, mites,as well as a systemic activity. Additionally, some of them also showfungitoxic effectiveness against phytophogenic fungi. The products maytherefore be used with success in crop protection and in the protectionof stored products, as well as in the hygiene field, against the mostdiverse animal pests.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (Rlzopalosiphum padi),the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphumsolanifolii), the currant gall aphid (C rptomyzus korschelti), the rosyapple aphid (Sappap/zis nzali), the mealy plum aphid (Hyalopterusarundinis) and the cherry black-fly (Myzus cerasi); in addition, scalesand mealybugs (Coccina), for example the oleancler scale (Aspidiotushederae) and the soft scale (Lecanium hesperidum) as well as the grapemealybug (Pseudococcus maritimus); thrips (Thysanoptera such asHercinotlzrips femoralis, and bugs, for example the beet bug (Piesmaquadrata), the red cotton bug (Dysdercus intermedius), the bed bug(Cimex lectularius), the assassin bug (Rhodnzus prolixus) and Chagas bug(Triatoma infestans) and, further cicadas, such as Euscelis bilobatusand Nephotettix bipunctatus; and the like. I

In the case of the biting insects contemplated herein,

above all there should be mentioned butterfly caterpillars (Lepidoptera)such as the diamond-back moth (Plutella maculipennis), the gypsy moth(Lymantria dispar), the brown-tail moth (Euproctis c/zrysorrhoea) andtent caterpillar (Malacosoma neustria); further the cab- (ProzleniaIituru), the ermine moth (Hyponomeum padella), the Mediterranean flourmoth (Galleriamellone/1a); and the like.

vAlso to be classed with the biting insects contemplated herein asbeetles (Coleoptera), for example the granary weevil (Sitop/zilusgranarius Calandra granaria), the Colorado beetle (Leptinotarsadecemlineaza), the clock beetle (Gaslrophysa viridula), the

mustard beetle (P/zaedon coelzleariae), the blossom beetle (Meligethesaeneus), the raspberry beetle (Byturus tomentosus), the bean weevil(Bruclzia'ius Acan thoscelide obtectus), the leather beetle (Derniestesfrischi), the khapra beetle (Trogoderma granarium), the flour beetle-(Tribalium castaneum), the northern corn billbug (Calandra or Sitophiluszeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm(Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilussurinamensis), and also species living in the soil, for examplewireworms (Agriotes spec.) and larvae of the cockchafer (Melolonthamelolontha); cockroaches, such as the German cockroach (Blattellagermanica), American cockroach (Periplaneta antericana), Madeirscockroach (Leucophaea or Rlzyparobia madeirae), oriental cockroach(Blatta orientalis), the giant cockroach (Blaberus giganteus) and theblack giant cockroach (Blaberus fuscus) as well as Henschoutea'eniaflexivitta: further, Orthoptera, for example the house cricket (Achetadomesticus); termites such as the eastern subterranean termite(Reticulitermes flavipes) and Hymenoptera such as ants, for example thegarden ant (Lasium niger); and the like.

The Diptera contemplated herein comprise essentially the files, such asthe vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly(Ceralitis capitata), the house fly (Musca domestica), the little housefly (Fannia canicularis), the black blow fly (Plzormia aegina) andbluebottle fly (Calliphora erytlzrocephala) as well as the stable fly(Stomoxys calcitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypzi), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius Tetranychus althaeae or Tetranychusurticae) and the European red mite (Paratetranyclzus pilosus Panonyc/zusulnu'), gall mites, for example the black currant gall mite (Erioplzyesribis) and tarsonemids, for example the broad mite (HemitarsonemusIatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornithodorus moubata); and the like.

When applied against hygiene pests harmful to health and to storedproducts, particularly flies and mosquitoes, the novel products are alsodistinguished by an outstanding residual activity on wood and clay, aswell as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide dispersible carrier vehicle such as gases,solutions, emulsions, suspensions, emulsiflable concentrates,

spray powders, pastes, soluble powders dusting agents, granules, etc.These are prepared in known manner, for

instance by extending the active. compounds withconventional pesticidedispersible liquid diluent carriers and/or dipersible solid carriersoptionally with the-use of carrier vehicle assistants, e.g. conventionalpesticide surface-active agents, including emulsifying agents and/ordispersing agents, whereby, for example, in the case where water is usedas diluent, organic solvents may be added as auxiliary solvents. Thefollowing may be chiefly considered for use as conventional carriervehicles for this purpose: aerosol propellants which are gaseous atnormal temperatures and pressures, such as Freon; inert dispersibleliquid diluent carriers, including inert organic solvents, such asaromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.),halogenated, especially chlorinated, aromatic hydrocarbons e.g.chlorobenzenes etc.), paraffins (e.g. petroleum fractions), chorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc. and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calciumcarbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying agents, suchas non-ionicand/or anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.), and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides,insecticidess, fungicides, bactericides and nematocide s, orrodenticides, herbicides, fertilizers, growth-regulating agents, etc.,if desired, or in the form of particular dosage preparations forspecific application made therefrom, such as solutions, emulsions,suspensions, powders, pastes, and granules which are thus ready foruse.

As cercems commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95% by weight, andpreferably 05-90% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in anamountsubstantially between about 0.000l-l0%, preferably 0.01l%, byweight of the mixture. Thus, the present invention-contemplates ov'erall compositions which comprise. mixtures of a conventional dispersiblecarrier vehicle such as 1) a dispersible inert finely divided carriersolid, and/or (2) adispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active effectiveamount of a carrier vehicle assistant, e.g. a surface-active agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 0.000l-%, and preferably OBI-9.5%, by weightof the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. averageparticle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare areneeded,.and often amounts only up to about 15 to 1000 g/hectare,preferably 40 to 600 g/hectare, are sufficient. In this process it ispossible to use highly concentrated liquid compositions with said liquidcarrier vehicles containing from about 20 to about 95% by weight of theactive compound or even the active substance alone, e.g. about 20100% byweight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects, acarids,nematodes and fungi and more particularly methods of combating at leastone of insects, acarids and nematodes which comprises applying to atleast one of correspondingly (a) such insects, (b) such acarids, (c)such nematodes, ((1) such fungi, and (e) the corresponding habitatthereof, i.e. the locus to be protected, a correspondingly combative ortoxic amount, i.e. an insecticidally, acaricidally, nem atocidally orfungicidally effective amount of the particular active compound of theinvention alone or together with a carrier vehicle as noted above. Theinstant formulations or compositions are. applied in the usual manner,for instance by spraying-atomizing, vaporizing, scattering dusting,watering, squirting, sprinkling,-

pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples EXAMPLE 1 Certitis test Solvent: 3parts by weight acetone Emulsifier: 1 part by weight alkylarlylpolyglycol ether To produce a suitable preparation of active compound, lpart by weight of the active compound is mixed with the stated amount ofsolvent containing the stated amount of emulsifier,'and the concentrateis diluted with water to the desired concentration.

2 cc of the preparation of the active compound are pipetted on to afilter paper disc of about 10 cm diameter. This is placed on a glass inwhich there are about 30'fruit,flies (Ceratitis capitata) and coveredwith a ssp ate.

After the specified periods of time, the destruction is determined as apercentage. 100% means that all the Table 1 (Ceraticts test)Concentration of active compound Active compounds stated amount ofemulsifier and the concentrate is diluted with water to the desiredconcentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dew moist and are then infested withcaterpillars of the diamond- Degree of destruction in 2 after in 1. 1day J "73 n (A) Cl 0.02 100 (Cli O) P-O 0.004 100 0.0000 30 (known)z-szss 2a (O ll O) p 0 c1 (known) o O 0.02 100 (c) n 0.004 65 "s 2 00.0008 0 (known) EXAMPLE 2 back moth (Plutella maculipennis).

Plutella test Solvent: 3 parts by weight acetone Emulsifier: 1 part byweight alkylaryl polyglycol ether To produce a suitable preparation ofactive compound, 1 part by weight of the active compound is mixed withthe stated amount of solvent containing the After the specified periodsof time, the degree of destruction is determined as a percentage: 100%means that all the caterpillars are killed whereas 0% means that none ofthe caterpillars are killed.

The active compounds, the concentrations of the active compounds, theevaluationtimes and the results can be seen from Table 2:

I Table 2 (Plut ella teat) Concentration of active compound Activecompounds Degree of des cruc;

tion in 7. after EXAMPLE 3 Piesma test Solvent: 3 parts by weightacetone Emulsifier: 1 part by weight alkylarylpolyglycol ether Toproduce a suitable preparation of active compound, 1 part by weight ofthe active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate isdiluted with water to the desired concentration.-

Active compounds Beet leaves (Beta vulgaris) are sprayed with thepreparation of the active compound until dripping wet and are theninfested with beet leaf bugs (Piesma quadrata).

After the specified period of time, the degree of destruction isdetermined as a percentage. 100% means that all the beef leaf bugs werekilled. 0% means that none of the beet leaf bugs were killed.

The active compounds, the concentrations of the active compounds, theevaluation time and the results can 40 be seen from the following Table3:

Table 3 concatenation of active compound .Degree of destruction in Zafter in 7. 3 days i ilk i c a 0 P 0 (known) (c n o 1= 0 0.0008 70EXAMPLE 4 Euscelis test Solvent: 3 parts by weight acetone Emulsifier: 1part by weight alkylarylpolyglycol ether To produce a suitable,preparation of active compound, 1 parts by weight of the active compoundis mixed with the stated amount of solvent containing the stated amountof emulsifier and the concentrate is diluted with water to the desiredconcentration.

Broad bean plants (Vicia faba) are sprayed with the preparation of theactive compound until dew moist and are then infested with cicadas(Euscelis bz'lobatus).

After the specified period of time, the degree of destruction isdetermined as a percentage. 100% means that all the cicadas were killedwhereas 0% means that none of the cicadas were killed.

The active compounds, the concentrations of the active compounds, theevaluation time and the results can be seen from the following Table 4:

Table 4 Euacelis test) Active compounds EXAMPLE 5 Doralis test (systemicaction) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weightalkylarylpolyglycol ether To produce a suitable preparation of activecom pound, 1 part by weight of the active compound is mixed with thestated amount of solvent containing the stated amount of emulsifier, andthe concentrate is diluted with water to the desired concentration.

Bean plants (Vicia faba) which have been heavily infested with the beanaphid (Doralidfabae) are watered with the preparation of the activecompound so that the preparation of active compound penetrates into thesoil without wetting the leaves of the bean plants. The active compoundis taken up by the bean plants from the soil and thus reaches theinfested leaves.

After the specified period of time, the degree of destruction isdetermined as a percentage. 100% means Degree of destruction in Z afterin Z 3 days 9 (A) E N 01 0.1 100 (cn 0) 1 0 0.02 60 (known) C c H o c1.1

( 2 5 )2? O 0.02 so (known) I 0.1 100 E N\ 0.02 100 1 0 0.004 60 0.1 1000.02 100 s in 0.000 100 (921,505; o 0.0008 100 9 I 0.1 100 3) 0 N\ 0.02100 5 i O 0.004 100 I I x s :z J (4) '1 0 c n 0 0.004 100 that all theaphids are killed; means that none of the aphids are killed. 1 I I Theactive compounds, the concentrations of the active compounds, theevaluation time and the results can be seen from the following TableTable 5 (Qoralis test/sys temic action) "Concentration of activecompound Active compounds tained' is diluted with water to the desiredconcentration. 7 i

Bean plants (Phaseolus vulgaris), which have a height of approximately.30 cm., are sprayed with the prep- 5 aration of the active I compounduntil dripping wet.

Degree of destruction in 7. after in Z 0 days I 5 ii (A) (cn3o)2i; 0 Cl0-1 0 7 (known) s 1'; g tc u m i'. 0 c1 0.1

(2) s 0.1 10o (c11 o) i' 0 (c n o i' q o (3'). v 9" o.1 so' I q a y l I2 g J: 4 1 :--o. I 0.1 V M22 5 0. .49 v

E AM 6 These bean plantsare heavily infested with spider mitesTetranychus test Solvent: 3 parts by weight acetone Emulsifier: l part.by weightalkylaryl polyglyco'l ether stated amountof emul'sifier andthe concentrate so ,ob-'

(Temu'zychus 'ui'ticae) in all stages of development.

After the specified periods of time, the effectiveness of thepreparation of active compound is determined .by counting the deadmites. The degree of destruction thus obtained is expressed as apercentage: means that all the spider mites are killed whereas 0% 5means that none of the spider mites are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 6:

'llble 6 (Tetranzchus test) Concentration of Active compound-n activecompound Degree of deatruc tion in 1 after 2 days Critical concentrationtest/soil insects Test insect: cabbage root fly maggots (Phorbiabrassicae) Solvent: 3 parts by weight acetone Emulsifier: 1 part byweight alkylarylpolyglycol ether To produce a suitable preparataion ofactive compound, 1 part by weight of active compound is mixed with thestated amount of solvent, the stated amount of emulsifier is added andthe concentrate is diluted with water to the desired concentration. Thepreparation of .active compound is intimately mixed with soil. The

' neuvdco 'smna active compound per unit volume of soil, which is givenin p.p.m. (for example mg/l), is decisive. The soil is filled into potsand the pots are left to stand at room temperature. After 24 hours, thetest animals are put into the treated soil and, after a further 48hours, the degree of effectiveness of the active compound is determinedas a percentage by counting the dead and living test insects. The degreeof destruction is 100% when all the test insects have been killed; it is0% when exactly as many test insects are still alive as in the case ofthe control.

The active compounds, the amounts applied and the results can be seenfrom the following Table 7:

EL -Ll (Soil. insecticides) (constitution) centration of active compoundin ppm of- 1) Y 100 100 100 too 15 o-a-P(oc n oc n Table 7 Continued(Soil insecticides) Active compound (constitution) Degree of destructionin 1 with a concentration of active cowound in ppm of known comparativeagents:

ll 0-P( 00 K 2 ii E 100 0-P( OCH; 2

(known) EXAMPLE 8 Critical concentration test Test nematode: Meloidogynesp.

Solvent: 3 parts by weight acetone Emulsifier: 1 part by weightalkylarylpolyglycol ether To produce a suitable preparation of activecompound, 1 part by weight of active compound is mixed with the statedamount of solvent, the stated amount of emulsifier is added and theconcentrate is diluted with water to the desired concentration.

The preparation of active compound'is intimately mixed with soil whichis heavily infested with the test nematodes. The concentration of theactive compound Active compound (constitution) in the preparation is ofpractically no importance; only the amount of active compound per unitvolume of soil, which is given in p.p.m., is decisive. The soil isfilled into pots, lettuce is sown in and the pots are kept at agreenhouse temperature of 27C. After 4 weeks, the

O lettuce roots are examined for infestation with nematodes, and thedegree of destruction of the active compound is determined as apercentage. The degree of effectiveness is 100% when infestation iscompletely avoided; it is 0% when the infestation is exactly the same asin the case of the control plants in untreated soil which has beeninfested in the same manner.

The active compounds, the amounts applied and the results can be seenfrom the following Table 8:

Table a' (News tocides a eloidogme incoggita) Degree of destruction in 2with a concentration of active compoimd EXAMPLE 9 LD test Test animals:Blatta orientalis Solvent: acetone 2 parts by weight of the activecompound are dissolved in 1000 parts by volume of the solvent. Thesolution so obtained is diluted with further solvent to the desiredconcentrations.

2.5 ml of the solution of the active compound are pipetted into a Petridish. On the bottom of the Petri dish there is a filter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used. 10 test animals are then placed in thePetri dish and it is covered with a glass lid.

The condition of the test animals is observed 3 days after thecommencement of the experiments. The de- 20 struction is determined as apercentage.

The active compounds, the concentrations of the active compounds, thetest animals and the results can be seen from the following Table 9:

EXAMPLE 10 Mosquito larvae test are placed in glass vessels and about 25mosquito larvae are then placed in each glass vessel.

After 24 hours, the degree of destruction is determined as a percentage.100% means that all the larvae are killed. 0% means that no larvae atall are killed.

The active compounds, the concentrations of the active compounds, thetest insects and the results can be seen from Table 10:

Table 9 (1.0 teat) Active compounds Concentration of Destruction activecompound in 1 in Z c1 Y E o 1 -(0cH 2 (known) 2 0.2 100 P-(OCH 0.02 100Table 10 (@sguito larvae test) Degree of Active compotmd Concentrationof active compound destruction in the solutim in 7. in I 0.001 100 (A)09 N s 0.0001 7 100 o (oc 3)2 0.00001 (known) 2 1% EXAMPLE 1 1 1.1),...test Test insects: Sitaphilus granarius (granary weevils) Solvent:acetone 2 parts by weight of the active compound are dissolved in 1000parts by volume of the solvent. The solution so obtained is diluted withfurther solvent to the desired concentrations. v 2.5 ml of the solutionof the active compound are pipetted into a Petri dish. On the bottom ofthe Petri dish .there is a filter paper with a diameter of about 9.5 cm.

The Petri dish remains uncovered until the solvent has completelyevaporated. The amount of active compound per squre meter of filterpaper varies with the concentration of the solution of active compoundused. About 25 test insects are then placed in the Petri dish and it iscovered with a glass lid.

The condition of the test insects is observed 3 days after thecommencement of the experiments. The destruction isdetermined as apercentage.

The active compounds, the concentrations of the active compounds, thetest insects and the results can be seen from Table l 1:

Table 11' test) 22- EJQAMPLE l2 LT test for Diptera Test animals: Aedesaegypti Solvent: acetone 2 parts by weight of active compound aredissolved in 1000 parts byvolume of solvent. The solution so obtained isdiluted with further solvent to the desired lower concentrations.

The condition of the test animals is periodically observed. The timewhich is necessary for a 100% destruction is determined.

The test animals, the active compounds, the concentrations of the activecompounds and the periods of Active compounds Concentration ofDestruction active compound in Z in I.

Table 12 (1.1 tent: for Diptera) Concentration of The followingcompounds are prepared by processes analogous to that given above:

Active compounds LT active compound 1 in the solution (A) 01 'f; y v 0.2120' 0 .?(0CH 0.02 180' (known) 0 l N (B) 01 L 0.2 60 I p(oc n 0.02 120(known) 0 @T' I 0.2 so s 0.02 60' 0.002 120' ((M3)? 0.0002 180' Thepreparative process of the present invention is Formula illustrated inand by the following Example.

N EXAMPLE l3 3) f b-floc n 5 2 o c (1) 6-1 (0c a @E n g 2 5 2 l (2) Io-rtocrg); 45 g of potassium carbonate are added to a solution of 0.3mole (41 g) of 3-hydroxy-l,3-benzisoxazole in 250 ml of acetonitrile; 75g of 0,0-diethylthionophos- 0 phoric acid diester chloride are thenadded at 30 (4) (I 35C and heating to 70 80C is effected for a further 2hours. After cooling, the mixture is taken up in ben- 5 zene, extractedwith water, the benzene phase is separated, dried, evaporated, and theresidue is slightly distilled.

The yield is 68 g 76% of the theory. n =l.5238

Calc. for C H O NSP (molecular weight 287): 10.8 11.2 4.88% Found: 10.7211.89 4.38%

Refractive index may be effected by a process analogous to thatdescribed in German Published Specification 1,157,231.

and

and a diluent therefore.

2. A composition according to claim 1, wherein said ester is O ,0-dimethyl-O-benzisoxazol( 3 )ylthionophosphoric acid ester of theformula T i (cn 1 0 3. A composition according to claim 1, wherein saidester is Q,P-diethyl-O-benzisoxazol( 3 )ylthionophosphonic acid ester ofthe formula 4. A method of combating insects, acarids or nematodes whichcomprises applying to the insects, acarids or nematodes or to a habitatthereof an insecticidally, acaricidally or nematocidally effectiveamount of a benzisoxazolo(thiono)phosphoric(phosphonic) acid esterselected from the group consisting of and 5. The method according toclaim 4 wherein said ester is 0,0-dimethyl-O-benzisoxazol( 3)ylthionophosphoric acid ester of the formula o:O- 3 15 I ((23 0);? o

6. The method according to claim 4 wherein said ester isO,P-diethyl-O-benzisoxazol( 3 )ylthionophosphonic acid ester of theformula

1. AN INSECTICIDAL, ACARICIDAL OR NEMATOCIDAL COMPOSITION COMPRISING ANINSECTICIDALLY, ACARICIDALLY OR NEMATOCIDALLY EFFECTIVE AMOUNT OF ABENZISOXAZOLO(THIONO)PHOSPHORIC(PHOSPHONIC) ACID ESTER SELECTED FROM THEGROUP CONSISTING OF
 2. A composition according to claim 1, wherein saidester is 0, 0-dimethyl-0-benzisoxazol(3)yl-thionophosphoric acid esterof the formula
 3. A composition according to claim 1, wherein said esteris O, P-diethyl-O-benzisoxazol(3)yl-thionophosphonic acid ester of theformula
 4. A method of combating insects, acarids or nematodes whichcomprises applying to the insects, acarids or nematodes or to a habitatthereof an insecticidally, acaricidally or nematocidally effectiveamount of a benzisoxazolo(thiono)phosphoric(phosphonic) acid esterselected from the group consisting of
 5. The method according to claim 4wherein said ester is O,O-dimethyl-O-benzisoxazol(3)yl-thionophosphoricacid ester of the formula
 6. The method according to claim 4 whereinsaid ester is O,P-diethyl-O-benzisoxazol(3)yl-thionophosphonic acidester of the formula